Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D1/00—Treatment of filament-forming or like material
  • D01D1/02—Preparation of spinning solutions
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/0007—Electro-spinning
  • D01D5/0015—Electro-spinning characterised by the initial state of the material
  • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
  • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4282—Addition polymers
  • D04H1/4291—Olefin series
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
  • D04H1/43825—Composite fibres
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
  • D04H1/43838—Ultrafine fibres, e.g. microfibres
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
  • Y10T442/681—Spun-bonded nonwoven fabric

Definitions

• Fiber spinning is often the processing method of choice in long chain polymers because of the subsequent chain alignment that occurs during the shear and windup process. This alignment can give rise to highly anisotropic electrical, mechanical and photonic properties.
• Commercial spinning lines need large (5-10 lbs) quantities of starting material in order to produce melt-spun fibers. This limits the candidates for investigation to those that are made in sufficiently large quantities and/or those that do not degrade at elevated temperatures, in the case of melt spinning.
• Solution spinning is possible as an alternative method but has been reserved for those polymers that dissolve in volatile and often times aggressive solvents (e.g., KBVLAR ® in sulfuric acid).
• KEVLAR ® is a polyamide, in which all the amide groups are separated by /r ⁇ r ⁇ -phenylene groups, that is, the amide groups attach to the phenyl rings opposite to each other, at carbons 1 and 4 and is manufactured by D ⁇ Pont), in sulfuric acid),
• Electrospinning an offshoot of electrospraying, can. be used to spin spider-web type fibers (see Figures 1-3) for characterization and testing of their mechanical and surface properties.
• the fibers produced during the electrospinning process are microscale and nanoscale, with diameters ranging (D.
• Electrospinn ⁇ ng is a simple method that can prepare fibers with submicron diameter using electrostatic force.
• Submicron fibers prepared by this technique have recently come under intense scientific study due to wide ranging potential applications including filtration, optical fibers, protective textiles, drug delivery system, tissue engineering scaffolds, and gas separation membranes etc.
• Many polymers, synthetic and natural, have been successfully spun into nano-, and/or micron-si2ed fibers from polymer solution and melt.
• polyolef ⁇ n (CH 2 -CHb) 0J poly- ⁇ -olefin (CH 2 ⁇ (R-CH)) n; with R aliphatic, aromatic or cyclic groups, their copolymers and/or their polymer blends are important commercial polymers, very limited work on the electrospinning of polyolefins, poly- ⁇ -olefins, their copolymers and/or their polymer blend fibers exists.
• polyolefins, poly- ⁇ -olefuis, their copolymers and/or their polymer blends have limited solubility due to their excellent chemical resistance and non-polar structure, and hence are not easy to electrospin from solution. All investigations thus far have used melt- electrospinning.
• the invention relates to a process for producing a porous membrane with polyolefin classes of polymers using the electrospinning process.
• These polyolefin membranes and/or membranes made from poly- ⁇ -olefin, their copolymers and/or their polymer blends have a high surface area, small pore size, soft feel., flexibility and possess the possibility of producing 3-diment ⁇ onal structures for use in filtration, protective textiles and gas separation etc.
• Polyolefins and poly- ⁇ -olefms like polyethylene, polypropylene, poly-1- butene (PB), poiy-1-pentene,, poly-1-hexene, poly(3-methyM ⁇ butene), poly(4-methly ⁇ 1-pentene) (PMP) 5 poly(4-methyl»l-hexene), poly(5-methyH-he ⁇ tene) ? etc and their copolymers and polymer blends consist of hydrocarbon chains of varying lengths , etc, and are in general and/or special use in many industrial applications.
• polyolefm, poiy- ⁇ -olef ⁇ n, their copolymers and/or their polymer blends are completely dissolved in a raulti-compo ⁇ ent solvent system to form a clear or transparent solution indicating that gelation has not occurred when heating from room temperature to a higher temperature depending on the polymer type, molecular weight and solvent system used.
• Room temperature is approximately 23 0 C.
• Upon cooling slowly from a temperature higher than room temperature to 25 0 C-SO 0 C under ambient conditions results in a clear solution for electrospinning (K-H Lee, S. Givens, D. B. Chase and J. F. Raboit, Polymer 2006, 47, 8013 ("Lee”))
• Solubility of polyolefin class polymers depends strongly on the chemical structures and molecular weight.
• poly(methyl-I-styrene) and polystyrene(PS) solutions can be prepared at room temperature while polyethylene, polypropylene, polybutene, and poly(4 ⁇ methyl-l-pentene).,etc solutions can not be prepared at room temperature.
• These polymers require heating for preparation of clear solutions for electrospinning.
• the polymer component is a single polyolefin or a mixture of polyolefins, where the polyolefins also include polyolefin copolymers and/or modified polyolefins. Mixtures of different polyolefins are very interesting due to varying physical properties such as mechanical, physical and thermal characteristics.
• thermal characteristics can be influenced, while adding certain amounts of a polyolefin with a high molecular weight can increase mechanical properties.
• high molecular weight polyolefins must be soluble in the solvent used.
• polyolefins, poly- ⁇ -olefins, their copolymers and/or their polymer blends have good chemical resistance and require high temperature (above 100 0 C except poly( ⁇ -methy! styrene)) to prepare the clear solutions. Solutions turbid at lower temperature eventually form a gel. [000014]
• FICl shows a field-emission scanning electron microscope (FE-SEM) image of an electrospun polypropylene fiber membrane from cyclohexane, acetone and DMF (80/10/10 w/w/w/ - weight %) according to example 1 at x500 magnification.
• FE-SEM field-emission scanning electron microscope
• FIG.2 shows a field-emission scanning electron microscope (FE-SEM) image of an electrospun poly(l-butene) fiber membrane from cyclohexane, acetone and DMF (80/10/10 w/w/w/ - weight %) according to example 1 at x250 magnification.
• FIG.3 shows a field-emission scanning electron microscope (FE-SEM) image of an electrospun poly(4-methyl-l-pentene) fiber membrane from cyclohexane, acetone and DMF (80/10/10 w/w/w/ - weight %) according to example 1 atxlOOO magnification.
• FE-SEM field-emission scanning electron microscope
• FIG 4 contains the schematic diagram of electrospinning results and FE- SEM images of as-spun PMP fibers from solutions of PMP in (A) cyclohexane, (B) a mixture of cyclohexane and acetone (80/20, w/w — weight percent)), (C) a mixture of cyclohexane and DMF (80/20, w/w - weight %) and (D) a mixture of cyclohexane, acetone and DMF (80/10/10, w/w/w-weight %).
• the arrows in Figure 4C illustrated curled and/or twisted fibers structures.
• FIG.5 shows field-emission scanning electron microscope (FE-SEM) images of an electrospun fiber membranes of blends (PB/PMP) from cyclohexane, acetone and DMF (80/10/10 w/w/w/ - weight %) according to example 1 atxSOO magnification, (A) PB/PMP (75/25), (B) PB/PMP (50/50) and PB/PMP (25/75).
• FE-SEM field-emission scanning electron microscope
• FIG. 6 is a schematic of an electrospinning process with continuous supplying system.
• polyolefin polymers are completely dissolved in a multi-component solvent system to form a clear solution when heated preferably to 50 0 C - 100 0 C depending on the solvent type, the polymer type and the molecular weight. Cooling the polymer solutions slowly under ambient conditions to 25°C - 50 0 C depending on the solvent type, the polymer type and polymer concentration results in clear solutions for electrospinning.
• Tailoring the multi-component solvent system with a blend of solvent and non-solvent for the specific polyolefin class polymer allows for a disruption of chain-chain interactions yielding a clear solution for electrospinning at room temperature in polypropylene, polybutene, and poly (4- melhyl-l-pen-tene),etc. systems .
• AH other work on electrospinning of polypropylene, polybutene, and poly (4-methy 1-1- pentene),etc systems has been performed in melt electrospinning without the presence of solvent.
• the invention has potential applications in filtration of liquids, gases and molecular filters. Reinforcement of composite materials, protective clothing, protective masks, biomedical application such as medical prostheses, tissue engineering templates, wound dressing, drag delivery systems, and pharmaceutical compositions, cosmetic skin care and cleaning etc. are additional applications.
• Clear solutions an indicator that gelation has not occurred in polyolefins, poly ⁇ olefms, their copolymers and/or polymer blends, can be obtained by dissolving the polymer in a good solvent and/or in a mixture of solvent and non-solvents at room temperature up to totemperatures at which the solvents boil depending on the polymer concentration, molecular weight and polymer type.
• room temperature 25°C
• the fibers are made from a polymer solution by an electrospinning process as described in Reneker, US 4,323,525, US 4,689,525, US 20030195611, US 20040018226, and US 20010045547, which are incorporated herein by reference in their entirety for all useful purposes.
• the polymers that are preferably used are listed in Huang, US 20030195611, US 20040037813, US 20040038014, US 20040018226, US20040013873, US 2003021792, US 20030215624, US 20030195611, U S 20030168756, US 20030106294. US 20020175449, US20020100725, US20020084178 and also in the following U. S publications, US 20020046656, US 20040187454, US 20040123572, US 20040060269, US 20040060268 and US 20030106294. All these publications are all incorporated by reference in their entireties for all useful purposes.
• the preferred solvents that may be used are (a) a high- volatility solvent group, including acetone, chloroform, ethanol, isopropanol, methanol, toluene, tetrahydrofuran, water, benzene, benzyl alcohol, 1,4-dioxane, propanol, carbon tetrachloride, cyclohexane, cyclohexanone, methylene chloride, dichloromethane, phenol, pyridine, trichloroethane, acetic acid; or
• a relatively low-volatiie solvent group including N,N-dhnethyl formamide (DMF), dimethyl sulfoxide (DMSO) 5 N,N-dimethylacetaraide (DMAc), 1- methyI-2-pyrrolidone (NMP), ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC)., acetonitrile (AN), N-methylmorpholine-N ⁇ oxide, butylene carbonate (BC), 1,4-butyrolactone (BL), diethyl carbonate (DEC), diethylether (DEE) 5 1,2-dimethoxyethane (DME), l,3-dimethyl-2-imidazolidinone (DMI), 1,3-d ⁇ oxolane (DOL), ethyl methyl carbonate (EMC), methyl formate (MF), 3-methyloxazolidin-2-on (MO), methyl propionate (MP), 2-methyletetrahydr
• DMF N,N
• Electrospinning or electrostatic spinning is a process for creating fine polymer fibers using an electrically charged solution that is driven from a source to a target with an electrical field. Using an electric field to draw the positively charged solution results in a jet of solution from the orifice of the source container to the grounded target. The jet forms a cone shape, called a Taylor cone, as it travels from the orifice.
• the cone becomes stretched until, near the target, the jet splits or splays into many fibers prior to reaching the target. Also prior to reaching the target, and depending on many variables, including target distance, charge, solution viscosity, temperature, solvent volatility, polymer flow rate, and others, the fibers begin to dry. These fibers are extremely thin, typically measured in nanometers. The collection of these fibers on the target, assuming the solution is controlled to ensure the fibers are still wet enough to adhere to each other when reaching the target, form, a randomly oriented fibrous material with extremely high porosity and surface area, and a very small average pore size.
• the basic components required for solvent electrospinning are as follows: A polymer is mixed with a solvent to form a solution having desired qualities. The solution is loaded into a syringe like container that is fluidly connected to a blunt needle to form a spinneret. The needle has a distal opening through which the solution is ejected by a controlled force, represented here in a simplified manner as being supplied by a plunger but can be any appropriate controllable variable rate fluid displacement system and should be automated to ensure accurate flow rates, [000033] The electrospinning process is carried out at temperatures ranging from a lower limit at which the solvent freezes to an upper limit where the solvent evaporates or the polymer degrades chemically. [000034] Examples Example 1
• PMP Poly(4-methyl-l ⁇ pentene)
• a choice of solvent quality for the solution used for electrospnning can have a dramatic effect on the spinnability of fibers and on their morphological appearance.
• solvent systems cyclohexane, cyclohexane/acetone mixture, cyclohexane/dimethyl formamide (DMF) mixture and cyclohexane/acetone/DMF mixture.
• electrospim fibers with different morphologies including round, twisted with a roughened texture, curled and twisted-ribbon shapes were formed.
• the fiber shape and morphology depended strongly on the type and amount of non-solvent used.
• FIG.5 shows field-emission scanning electron microscope (FE-SBM) images of an electrospun fiber membrane of blends (PB/PMP) from cyclohexane, acetone and DMF (80/10/10 w/w/w/ - weight %) according to Example 1 at x500 magnification, (A) PB/PMP (75/25), (B) PB/PMP (50/50) and PB/PMP (25/75). In all cases, twisted flat fibers are produced.
• FE-SBM field-emission scanning electron microscope

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
• Nonwoven Fabrics (AREA)
• Artificial Filaments (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Woven Fabrics (AREA)

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• 2006
  • 2006-11-22 CA CA 2631419 patent/CA2631419A1/en not_active Abandoned
  • 2006-11-22 AT AT06846374T patent/ATE495875T1/de not_active IP Right Cessation
  • 2006-11-22 US US11/562,797 patent/US8083983B2/en not_active Expired - Fee Related
  • 2006-11-22 WO PCT/US2006/061206 patent/WO2007062393A2/en not_active Ceased
  • 2006-11-22 JP JP2008542518A patent/JP2009517554A/ja active Pending
  • 2006-11-22 DE DE200660019774 patent/DE602006019774D1/de active Active
  • 2006-11-22 AU AU2006318206A patent/AU2006318206A1/en not_active Abandoned
  • 2006-11-22 KR KR1020087014116A patent/KR20080083637A/ko not_active Withdrawn
  • 2006-11-22 EP EP20060846374 patent/EP1957256B1/de not_active Not-in-force
  • 2006-11-27 TW TW95143681A patent/TW200823252A/zh unknown

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